Äîêóìåíò âçÿò èç êýøà ïîèñêîâîé ìàøèíû. Àäðåñ îðèãèíàëüíîãî äîêóìåíòà : http://www.students.chemport.ru/materials/inorg/inorg9.pdf Äàòà èçìåíåíèÿ: Thu Jan 15 17:55:07 2009 Äàòà èíäåêñèðîâàíèÿ: Mon Oct 1 21:37:48 2012 Êîäèðîâêà: Ïîèñêîâûå ñëîâà: m 63

..

!

"

#.$.

% & (Li, K) ­(

/ . . ., . . ., % 3! . . ., 2
, 2001

: 1.2. : . ! !., 2.#.


.
I. II.
................ 1. : 2. % 3. .................................................................................. ( ......................... ............................................................. 4 6 12 14 .................................................... 1. $ 2. % 3. $ ( & ! ....................................... ............................... 14 14 17 25 26 ................................................................ .................................................................................. 3 .............................................. 4

III.

.......................................................................................

IV. V.

.................................................................................

2


I.
> ! , 3 3 3 C C ! ( " ! A

.
1990" " .$ C ( ! " " & (broken %60). , ! C , , K ! " . & ­( (Li, K). ! C C , B " ,! . ! ! C ! B ! . , B. ! ! ! ! B

( ( " N B "

.J

3


II.
1. !
: " , A ! "" 56- " , ! P A, ( ". Buckminsterfullerene). / , " & " N & N%
60

.
.
­ , K / B , 6- " , ) [2,5]. A / J " : 5Bucky , ! %
60

( .), , P. ! A " ! , %
70

" C A (%R#) %

! 80- " . 1996 " (

( 20 .: %70, ! . , ),

Q , P. %

60

.

!
90

%36, C76, C78, C84, C ­ B ! [1]. " , 6- " ball), %
60

[1,3]. " ( ! (! ,! %
60

& ,

&

), C B B

.$

! .$ B "

" &B ! B

C C ( ". !

C A & A 1 .` A [2,12], ! " % A ! B :K " C ! 255 ! (sc) [12].
60

" %60. & ! =14.17å [6], ! ! " 1.4 K ! ,! " ! ( A ! % !

,

%70, ! K %
60

[1], 6.99 K / [2]. 1.68 "/ ! % " "
60 3

[12]. 3

(fcc)

B [11]. % " ( ,

60

400°%, %

!

!

A 1000°% [5]. : ) [1, 2], ,!
4
60

!

B


C "

%

60

[2] (!

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, %60(%6/6)4 [12]). / .

P . 1. % , ! ( ! " , C : [2,3], " e ! ! ", " ! ! ! % ,
60

(å). %! ! ! ! & " ! ! C ! K , " !( ! " , B, K & ! -! ! ! % %60, B C 170°%
5
32

­ !

[12]. % " "

! R"

e . /!

! "

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," K

C ! B, / 200°% !

B

!

(

C %
60

!

!

"


" ", ! " ( " ( .3 C! . [2,5,17] ! , NO2, `1g# B! ! " ( .3 " ! " " %
60

[3]. ! " & B A !

!"

( !

, [1]. >

,

2.
P % % ! > " $ " ! 30 g ! (" K K ! ! ( , %60 ! K " B( B
3 60

#
! " ( C B A C , ! [1,6]. % & 1! N- A ! e ! A ( [6], A A [10]. % ! K %60, " ­( %
60

$
, " )­K ( ) "" C B ( K C ! ! ( " (

%
(

.

C C

[1]. B( ( -« ! B ! A ! . K .` ! ! ! , ( ! & . " [6]. 3 ! N- A ! ! K B 26% ", & .3 ( [5]. B ­ «" ». [8]. , , ! » C . !

B

" ,

! , C

! !

(

K C

6


g % ! %60 ­ ( & *0, * RbCs2C Rb2CsC Rb3C
60 60

& 1.

.

+ [3, 12] [1,6] [1,6] [6] [6] [6] [1, 12] [1] [1,6] [10]
, , & " !

, [10] / 14.493 14.436

-

a0 (å)

60 60

33 30-31 29 26-27 24 22-23 18-19* 18

KRb2C K2CsC % K2RbC
3 60 60

14.336, 14.364**

60 60

14.299 14.253

Cs3C

Na2CsC Na3C
60

60

10-12 -------------g ! "! [10] . A

14.132, 14.176** 14.183
" ( ! [9].

*% ** !

B! %
60

" 6 %60 !
4

, ,

C N- A " e -& [6,7]. 6 30% B . 2. !

K, Rb %

Cs [7]. g , ! % [6]. .1 A ,
6

60

6

60

3

%

60

N- A K Fleming K A, N [6]. % A . ( Rosseinsky [14]

4

%

60

%60 ­

e ,

-

& >N (bcc) ! C ! A

%60, ! " "

7


P . 2. %60, ­ % Na2C60 c Na #4%60 (A = K, Rb, Cs). (e) N - A K, Rb, Cs.

[10]. J A ( " . (a) N - A K ! & .()% #6%60 (A = Na, Ca). (f) >N - A

­ %60. (b) #3%60. (d) #6%60

%
> " ( " B( B C ! ! / 12 ! B B & , ! " A ( ! " .% .3 Li) ! , " %
60

4
!! . ! (B

%
A !

.

! ( ! .% & (10-30 ") ! ( " ! " B C ! ! ( ! C (B ! . B.3 , 3 B " ! B (B

! B! ( , .3). /
8

"B
3

200-400°% [6].

%

60


A [6]. 3 ! [9]. P .3. 1 ! g A [10] " % " , ! & C ! ( " ! ( . & 2! %
60

B ! , C ! ! ! ! ! (

! 20

(~1

),

" " . , ! , K .3 C B A ! " &"-

.

! "! . , ( [6]. $ ! & " K! . g & 2. ! " Rb6C60, . ! C ,K B

"

"

[10].

& A6C60 (A=K, Rb, Cs) Na6C
60

, °C 250-350 350-400 225, 400 200-250 10-15 6-7 3, 7 10-15
g=400°% [14]. A .

Rb4C60* A3C60, A4C60 (A=K, Rb, Cs)**
*3 ** ­3 ! g=225°%, "

­7 ! #6%60 %60

7

4
" " !& " . " !

%

.

( ,K . /!
9

B ! !

" B ! Na!

! !

,


" ! 330°% 1 C( 2( ( " & ! ! ! ! 2 C
3

[10]. g 9 ! #6% ), "
60 60

Na2C

60

B 10 ­ 15 # 2% . A .%

Na5Hg2 c C60 ! .
60

350°% ( C & & !

Na3C60 ­ ! - NaH. %60, NaH Na-

Na5Hg2 B , ! " ! ! !

!

A

#6%

B " [12]. 1 .3 ! 10%. #%
60

, ( ! ! > [6]. % " , ! C ! C! ! 300°%, ! K C ! , . Rb ). 3

B #3% ! B B #3%60, !
60

(

A B( " 50% [6]. ! A B( ,! ", %
60

%

60

%

60

C

B(

!

B !

.
" & " C ! Li C60, ! [15] . ( LiN3, C !

K K ! K ! C ! , ! C

. ,K (P(EO)8LiClO4). : =0.5, 2, 3, 4 Li4C60 12 [12, 17]. Li8C60

%
1 ( ! " & !
10

.
! , K, ! & " . [1] ( , ! " A !


! Na " 2 , ./ [1]. Li C60, ! Li %
60

! ! " 1 B , [15] ! ! 5 " % $ & (*)
60 60 60 60

A 4.5 ! (45000 B " (B ,! 5.5 3 9.6 19.4 (g . 3.). ! ! .P "

.) Na21C " C
60

Li50C60. 1 C

553-573 . g [15].

,

18

& 3.

8 (9, ) 5.5 5.5 5.5 5.5 18 . 13 . 13 . 30 8 . 25
50%.

& / C. d=7 / C. d=8 . . / C. d=7 . d=7

Li9.6C Li Li Li
19.2 13.8 19.4

553 573 553 553
& !

C C C

A

% &

! " Li9.6C60, Li
13.8

xP & Li C60, Li
19.2 19.4

! C60,

! !

! "

! A"

C60.

+
> C ! / " ! 3 A ! C ! ! .% .4! ! ! &

%
! C , [10]. "

.

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-%60. =3, 4, 6 %60. %
60

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-

C <3 !
11

1

! NaCl. z
3

&

:

1

%

60

%

60

+ %60.


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1

%

60

C

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[1] 50"

, [6,12], K

C(

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3.

9
/ " ,! 3) A

%

.
! %60Pt ! %
60

"
9

. ( B %60/ ( =2­26) g & 4. [13] /2

/! ­ 1-3 Pt h

C60Pd4. & "

/,

PdHy ! % %60Pt C60Pd
4. 9

(g

& 4.). " & 400-550 600-700 400-550 600-700 !

C C C C !

60 60 60 60

PtHx Hx + Pt Pd4. 9Hx Hx + PdHy .g ,

C % %60D8, C60D18 " %60D8, C60D18
60

C" ! ,! ( C60D36 373-773 ( K ! ) " C60D36.

D2=15 ) a0 A

!! B .3 N! A [13]. A

1.423, 1.448

1.500

12


P ! " & . / , ! ! "

4. : K " B

" " ! !( ", ! ! ! " C A ( .

-%

60

[3]. 3 ! %60z(%60+ 3%60). 1 =3 =4 ! ,! .3 " " K .3 A 450

! ! " !

g2= 425 3 C .3 B" !

" ! .

13


III.
1. ;$ <
P " %60/18.7, ! A [13]. 3 ! A " " P ( ! " 3). & & . " " .3 ! A ! " ", C ! A ! a0=1.476 .3

.
# %=
, ". ~

. %
"

.
($ ) 700°%. C ! (% B , C ! « B! " " , C » .% ( . " "
60

J.3. g

! ! ! " B ! broken) & !

2. %
1 & B( 3 ! 15 ! B .5. % & " 1­ ­ % ! . 10 !
14

4
! " 0.0226 " ! ! .h ( " (5*10-3 g ! ) .# ! " ! ! ! " !

%

.
& [6] (22.6 ") , C ! B! . .1 ! B A . ( .5).

! 2. 1 ! ./ !

!

" . ,2 ! 270±5°%.


3 ! ! " .3 !

! ! ( . "& .% .% &! "

%
3 ! ! 3 K! ! C. B ! , 7. ! ! B Li20C60. P A , B( ! " A ! " ! ! « & ». %

$
! B(

.

.% 0.95"/
3

.h ! !

P . 7. % 1­ ,2­ h­

!

. , ! .

P
! ! 3 3
m( m( Li m( Li ) ( Li ) V( .) 20 = ) 60 m( + ( â µ ( Li ) , â µ (C ) .) =V( .) .) â

"
!.

.

:H :d
.

=6.18 =7
3

, ,

!.

:·

=0.95 "/
3

,

: ·Li=0.53 "/

,

.), ( .).

.) = d 2 (

3

,

A

,!

:

15


m(

.) =

d2( .) â H ( .) = 0.1679 20 â µ ( Li ) 1 + 60 â µ (C ) â ( Li ) ( .)

/ 1 , ! Li. ­ 1.0537 ", P ! B( B !

,

B 168

"!

! !

! 0.9966 ", !

.

0.0571 ". B :

LixC60*: x = 1 " !

( Li ) m( Li ) â 60 â µ (C ) = = 3 5 .4 . µ ( Li ) â m(C 60 ) (C 60 )

( « ! » 10*8 ! , .

! «! : »

! 10

80 !

.J

/ (12 - / «!
!

=/

!

*=4.74

)/2=/! J ». m 1 3.63 ! ­

=3.63

" d=10 , : m 1 4.74 ­ ,

« 10*8 ­ 0.0556",

» :

­ 0.169", =3.63*0.169=0.613",

=4.74*0.0556=0.263", " , ! & 4. " C WC, . " ! B & ,

1 .7. % ! & ! [15] ! B( & B !

16


P . 7. % ! . 1- " ! 3­ 4,5 ­ 6-" ( A & ! ! " !

« ! ,2-" ­ " " , 7,8

&»

«" " " ­! , .

», , , 9­

g . $ Li35.4C60 7 42.5 (4.3 3 ) & 310°% ( 583 ) 4

& 4.

3 " .3

! &

! P:# x P.

A

"

3. ;
1 "

%
"

=
! " (P:#). !

.
!

8!>.
C " & ! " " ! K"" C B( C C (! " , d .1 & " B
17

& .3 C ! ( " " " (" " .3 ! , B) C & C " " A

" ! d C CB ! ! B " )! J K"" & B ! B( & "

! B

! &

B)


B: 2dsin = , ( ! 1 " «1 P &. -3 » ($ ! ­ Cu K , ! " P:# d( ) ! &! ! A " ( .

"

" [16]. ! B " .# BB & !

)

&,

&

" !

=1.54178 å) " ( . 8-10) B(

;
1 " : &

%=
&

4%
"

.
! B(

P . 8. 1 ( 3

" !

& ), ! " "

" ­" !

.3 2* .

­

& (g

& 5.).

18


g P 2* 10.95 17.85 20.90 21.85 27.50 28.25 31.05 32.95 45.85 1 ! A , A : a0=14.12±0.01 å, A " %60. & " ! ( di(@ P:# .) (å) 8.080 4.969 4.250 4.068 3.243 3.159 2.880 2.718 1.979 " 1/d2=(h2+k2+l2)/a2, " ! -! ! " ( A / & I/I0(%) 67 98 100 33 17 26 22 21 12 A [18], ! : " . h, k, l 1, 1, 1 2, 2, 0 3, 1, 1 2, 2, 2 3, 3, 1 4, 2, 0 4, 2, 2 5, 1, 1 7, 1, 1

& 5.

;
P 3 C (" ! %60*, >/
2 3

%
P:# " ! %>3, ! BC ! ). 3 & (

.
! . 9.) ! ! ! ! C C , %60 (g & ( " C & ! ( & 8. )

%60*. J B

«%60broken» 7.).


g % ! &
3 4 6

& 7.

A N >Ng >N

-

C( , 14.253 11.886 11.390

[10]. (å)

% % %

60 60 60

g P 2* 10.12 17.30 17.80 19.00 19.30 20.40 20.70 22.20 24.80 27.10 29.40 30.70 31.40 33.50 35.21 36.90 37.09 38.70 39.30 40.50 45.92 P:# di(@ .) (å) 8.744 5.126 4.982 4.672 4.600 4.354 4.291 4.004 3.591 3.291 3.038 2.913 2.849 2.676 2.549 2.436 2.424 2.327 2.293 2.228 1.976 . I/I0(%) 64 98 100 96 96 86 84 77 52 43 56 39 36 37 29 28 29 27 28 33 23

& 8.

20


# ! " /:

C!
6

! %60. J ! ! a0=11.4±0.1 å

A A !

P . 9. 1

"

.

;
# ! 3 , " ! " ! " , " ( A ! .P

%
!

.
! " ,! ! , & Li , ! ! ! !
35.4

P:# ! !

x P& C 9.

! .10). 3 ("

A

C60* " ). / ! " !

! C

.

21


g P 2* 11.06 18.04 18.14 18.56 19.31 21.65 21.79 24.06 28.56 30.25 P:# di(@ .) (å) 8.002 4.916 4.890 4.781 4.597 4.105 5.078 3.698 3.125 2.955 . I/I0(%) 56 100 99 91 84 78 77 43 34 29

& 9.

P . 10. 1 J.$. 3 P

"

& Li

35.4

C60. ( & Li "
35.4

($ ) ! x P22

C

60

!


! ! C ! & ! x P 7Li
7 13

8 ! 4 " ! & ! ! Bruker) ! C B xP %60* A ! , &
13

! ! ., ! ! " ! ! & A C ­ 6645 x P. & B !

Bruker AC-200. %! : ! & ­ 6000
13

x P 7Li ! ­2 C 1024 x P. 3 ,
7

13

C

Li . 3

LINESIM ( ! & xP " . & ! C .> ,

!

xP .R &

Li (

P . 11. ` ! !& !! ! P !

! x P 7Li " LINESIM & 9267 &.

! " , . &

& .

" 13.7 . ., A

23


P . 11. ` ! !& !! P ! ! J.$. 3

! x P 7Li " LINESIM & 9267 &. ! " ! ! " ! .3 C . C ( !

! " , & .

& .

" 13.7 . ., A

" x P&.` ! C ( , " ! . &

/

24


IV.
1. 3 2. /
6

.
! & %60*. Li P:# ! A x P- ! . ! ! C ! Li
35.4 35.4

A "

%60 broken. " C60*.
6

3. % 4. % 5. % ! ! ! C

! ! ! C

%60* C

C60*, .

C

25


V.
pp. 1-134,

:

1. B. Sundqvist, Fullerenes under high pressures, Advances in Physics, 1999, vol. 48, ^1, 1 . W. Kratschmer, D.R. Huffman et al., Nature, 1990, Vol. 347, p.354, 2. `& ! , .5, .211, .: JP`, 1999, 3. J.H. Weaver, D.M. Poirier. Solid State Properties of Fullerenes and Fullerene-Based Materials, Solid state physics, 1994, vol. 48, pp. 1-108, 4. Buseck P.R., Tsipursky S.J., Hettich R., Fullerenes from the geological environment., Science, 1992, vol. 257, pp.215-217, 5. /.x. g ,/ " & , . 54, ., 1999, 6. C.M. Lieber, C.-C. Chen, Preparation of Fullerenes and Fullerene-Based Materials, Solid state physics, 1994, vol. 48, pp.109-148, 7. J.E. Fischer, Intercalation compounds of solid C60, Physics and chemistry of fullerenes, pp. 223-244, Kluwer Academic Publishers, Netherlands,1994, 8. `& ! , .2, .403, .: JP`, 1998, 9. L. Wang, H. Sekine et al., Fast preparation of superconducting K-doped C60 films, Chemical Physics Letters, 1999, vol. 305, pp. 85-88, 10. D.W. Murphy, M.J. Rosseinsky et al., Synthesis and Characterization of alkali metal fullerides: AxC60, The fullerenes, pp. 151-162, Pergamon Press, Oxford,1993, 11. K. Holczer, R.L.Whetten, Superconducting and normal state properties of the A3C60 compounds, The fullerenes, pp. 123-138, Pergamon Press, Oxford,1993, 12. A. Hirsch, The Chemistry of the Fullerenes, Thieme Medical Publishers, New York, 1994, 13. J.3. g >B CB , /.:. A " , #.3. >B , ! ,= > ?@A? ? ? : > B?D > , 2001, .70, ^2, . 149-166,

14. R.M. Fleming, M.J. Rosseinsky et al., Preparation and structure of the alkali-metal fulleride A4C60, Nature, 1991, vol. 352, pp. 701-703, 15. S. Menu, Contribution Þ I'Ètude de composÈs du C60 avec le lithium et le sodium, Þ forte proportion d'alcalins et ÈlaborÈs sous haute pression, UniversitÈ d'OrlÈans, France, 1999, 16. `& ! , .4, .242, .: JP`, 1995, 17. O. Zhou, D.E. Cox, Structure of C60 intercalation compounds, The fullerenes, pp. 123138, Pergamon Press, Oxford,1993, 18. . ., P " " " , .64-67, .: , 1991.

26